CN102964539B - The preparation method of porous magnetic polystyrene microsphere - Google Patents
The preparation method of porous magnetic polystyrene microsphere Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 14
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000005406 washing Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001291 vacuum drying Methods 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 14
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000004088 foaming agent Substances 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000004090 dissolution Methods 0.000 claims abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910015400 FeC13 Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 filters Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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Abstract
The invention discloses a kind of preparation method of porous magnetic polystyrene microsphere, (1) is by dry Fe3O4Magnetic nano-particle joins in ethanol water, after ultrasonic processing, adds VTES, then proceeds in the lump in reactor, under nitrogen protection, constant temperature stir ageing, product through washing, vacuum drying, pulverize; (2) get powder and the benzoyl peroxide mixing that step (1) obtains, add in the styrene that contains pore-foaming agent and crosslinking agent ultrasonic processing; (3) by polyvinylpyrrolidone and lauryl sodium sulfate ultrasonic dissolution in water; (4) liquid step (2) being obtained joins in the liquid that step (3) obtains, ultrasonic processing, the mixture obtaining is poured in reactor, and the reaction of intensification condensing reflux, obtains suspension, wash through magnet magnetic separating alcohol, magnetic separates pure water washing again, and brown color powdered product is ground to obtain in vacuum drying, then Soxhlet extracting, last vacuum drying, to obtain final product.
Description
Technical field
The present invention relates to a kind of preparation method of porous magnetic polymer microballoon, particularly porous magnetic polystyrene microspherePreparation method.
Background technology
Along with the development of life science, the compartment analysis that carries out fast and efficiently large biological molecule has more and more been subject to peopleAttention. The separation means that biological magnetic separation technique gets up as a kind of development in recent years has efficiently, quick, solventConsume and less, easily realize the fashionable biology of the advantages such as automation, biotechnology and biomedical sector. Biological magnetic separates and needsWant that ball-type is regular, uniform particle diameter, good dispersion, magnetic responsiveness be strong, has the magnetic ball of superparamagnetism. In order to make biological magneticIsolation technics is applied even more extensively, and should prepare the magnetic of surface with functional groups such as carboxyl, hydroxyl, epoxy radicals, amidosBall, is easily combined with different biological molecules with the magnetic ball of these functional groups.
Magnetic porous polymer microballoon is an important branch of magnetic polymer microsphere, and it refers to by certain method systemStandby a kind of magnetic polymer composite microspheres with loose structure, is a kind of novel functional material, and its character depends onThe character of inorganic magnetic material, macromolecular compound and recombination mechanism thereof, the magnetic that particularly different magnetisable materials showsThe varied property of character. For magnetic porous polymer microballoon, on the one hand, monomer polymerization or surface modification etc. is givenIts surperficial several functions group (as: OH ,-COOH ,-NH2,-CHO etc.), make it have hydrophily, biocompatibleProperty or other surface property; Secondly, it has stronger magnetic or magnetic responsiveness, is therefore convenient to magnetic and separates and magnetic steering;It also has the surface texture of porous in addition, and it is long-pending that therefore microballoon has larger surfaces externally and internally, and loose structure is all rightGive microballoon special application performance, therefore in affinity chromatography, the field such as immobilization and environmental project of enzyme has wideApplication prospect. Therefore, design and the magnetic porous material that synthesizes different structure has significant scientific meaning and application valencyValue.
At present, the existing report of preparing porous magnetic polymer microballoon is little, in order to obtain the porous magnetic that particle diameter is lessPolymer microballoon, to make it fully represent the advantage that small size microballoon is had, expands its range of application, and the present invention carriesSupply a kind of preparation method of porous magnetic polymer microballoon.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of porous magnetic polystyrene microsphere, the methodBe mainly to prepare magnetic microsphere by the finishing of magnetic particle and the method for microsuspension polymerization, ultrasonic high speed shear hasEffect promotion homogeneity and the stability of dispersion.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
The preparation method of porous magnetic polystyrene microsphere, it comprises the steps:
(1) by dry Fe3O4Magnetic nano-particle joins in the aqueous solution of ethanol, the ultrasonic processing of ultrasonic cleaning machineAfter 20 ~ 30min, to Fe3O4In suspension, dropwise add VTES (SG-151), then proceed in the lump reactionIn device, under nitrogen protection condition, stir ageing 12 ~ 24h, the Fe after the modification obtaining at 35 ~ 50 DEG C of constant temperature3O4MagneticNano particle through washing, vacuum drying, pulverize;
(2) get powder and benzoyl peroxide (BPO) mixing that step (1) obtains, add and contain pore-foaming agent and crosslinking agentStyrene solvent in, ultrasonic processing 0.5 ~ 1h, described perforating agent is the mixture of first benzene and heptane, described friendshipConnection agent is divinylbenzene;
(3) polyvinylpyrrolidone (PVP) and the ultrasonic processing of lauryl sodium sulfate (SDS) are dissolved in the water;
(4) oil-based liquid step (2) being obtained joins in the liquid that step (3) obtains, the ultrasonic processing of large power supersonic instrument5 ~ 10min is to fully disperseing, and the mixture obtaining is poured in reactor, after 70 ~ 80 DEG C of condensing reflux reaction 1.5 ~ 2h,Be warming up to again 80 ~ 90 DEG C of condensing reflux reaction 6 ~ 8h, obtain micro-bluish violet suspension, wash through magnet magnetic separating alcohol respectivelyWash, magnetic separates after pure water washing, and brown color powdered product is ground to obtain in vacuum drying, and brown color powdered product is carried out to SoxhletExtracting 24h, last vacuum drying, to obtain final product.
In step (1), Fe3O4Magnetic nano-particle can be according to existing routine techniques preparation, and concrete preparation method can joinExamine as follows:
By FeCl2·4H2O、FeC13·6H2O mixes with the mol ratio (mass ratio 1:2.7) of 1:2, is dissolved in 10～12 times of matterIn the water of amount, stir lower dissolving, logical nitrogen drives oxygen half an hour, is then warming up to 60 DEG C, under rapid stirring, adds rapidlyThe NH of amount3·H2O, system becomes black from transparent yellow green immediately. Be warming up to subsequently 90 DEG C, keep temperature 30min,Then drop to room temperature, add 3mol.L-1HCl regulates pH=4, leaves standstill product magnetic field separated and collected. The product of collectingUse deionized water dispersed with stirring, then magnetic field separates, and said process is repeated multiple times until without free Cl-, after vacuum drying,Grind into powder.
In step (1), in the aqueous solution of ethanol, the concentration expressed in percentage by volume of ethanol is 40% ~ 60%.
In step (1), for the aqueous solution of 1L ethanol, dry Fe3O4It is 8 ~ 12g that magnetic nano-particle adds quality.
In step (1), for 1gFe3O4Magnetic nano-particle, the addition of VTES is 1 ~ 2ml.
In step (1), mode of washing is first absolute ethanol washing 2 ~ 3 times, then deionization is washed 2 ~ 3 times.
In step (1) and (4), vacuum drying temperature is 40 ~ 60 DEG C.
In step (2), the powder that step (1) obtains and benzoyl peroxide in mass ratio 2 ~ 4:1 mix.
In step (2), the volume ratio 10 ~ 16:4:2:1 of styrene, toluene, normal heptane and divinylbenzene; ForThe powder that every 1g step (1) obtains, the use volume of divinylbenzene is 1 ~ 1.5ml.
In step (3), the mass ratio of polyvinylpyrrolidone, lauryl sodium sulfate and water is 5 ~ 8:1 ~ 3:1000;The mass ratio of the powder that polyvinylpyrrolidone and step (1) obtain is 1 ~ 2:1.
Step (1), to step (3), is ultrasonic wave dispersing and dissolving in conventional ultrasound cleaning apparatus. In step (4), ultrasonicPart is that 20KHz Ultrasound Instrument batch (-type) is ultrasonic, and ultrasonic time is 5 ~ 10min, and the intermittent time is 2 ~ 5 seconds/time.
In step (4), in Soxhlet extracting, the solvent of use is the ethanolic solution that adds hydrochloric acid, and the concentration of the hydrochloric acid adding is36 ~ 38wt%, the volume ratio of hydrochloric acid and ethanol is 1:75 ~ 1:30.
The porous magnetic polystyrene microsphere preparing is according to the method described above also within protection scope of the present invention.
Beneficial effect: the preparation method of porous magnetic polystyrene microsphere microballoon of the present invention, adopts one-step method to prepare porousMicroballoon, finishing process make magnetic particle and polymer bonding more abundant, ultrasonic technique distributes more magnetic particleAdd evenly, SEM, TEM(is shown in accompanying drawing) the preparation balling-up that intuitively characterizes magnetic porous microspheres is good, and size reachesBelow 20um, particle diameter narrow distribution, magnetic responsiveness is good. In this method, when stabilizing agent and emulsifying agent, add raisingThe stability of system, the microspherulite diameter narrow distribution of the preparation of Ultrasound Instrument, porous microsphere form is better, micropore distributes allEven, at immunoassay, the immobilization of enzyme, target administration, the fields such as cell separation have wide practical use.
Brief description of the drawings
Fig. 1 is the homemade magnetic Nano Fe arriving involved in the present invention3O4The TEM photo of particle.
Fig. 2 is the SEM photo of porous magnetic polystyrene microsphere of the present invention.
Fig. 3 is the TEM photo of porous magnetic polystyrene microsphere of the present invention.
Detailed description of the invention
According to following embodiment, the present invention may be better understood. But, those skilled in the art will readily understand, realExecute routine described content only for the present invention is described, and should also can not limit in claims described in detailThe present invention.
Embodiment 1: the preparation of material.
Cinnamic refining: extremely colourless with the NaOH aqueous solution cyclic washing of 200ml5wt%, to remove polymerization inhibitor,Distilled water washing three times, adds anhydrous CaCl afterwards2Dry, pack brown bottle into and save backup.
Refining of benzoyl peroxide (BPO): 10gBPO is dissolved in stirring and dissolving in 50ml chloroform, filters, and filtrate is drippedEnter in 100ml methyl alcohol, put into refrigerator and leave standstill, obtain white, needle-shaped crystals, with a small amount of cold methanol washing three times, room temperature is trueEmpty dry 10h, packs brown wide-mouth bottle into, and refrigerator cold-storage is for subsequent use.
Fe3O4The preparation of magnetic nano-particle: by 4.28gFeCl2·4H2O、11.70gFeCl3·6H2O is dissolved in 180mlIn water, stirring and dissolving, logical nitrogen is warming up to 60 DEG C after driving oxygen 0.5h, under rapid stirring, adds rapidly20.0mlNH3·H2O, system becomes black from transparent yellow green. Be warming up to subsequently 90 DEG C, keep 30min, thenLeave standstill cool to room temperature, add 3mol.l-1HCl regulates pH=4, leaves standstill, and after washing magnetic separation several final vacuum is dry,Grind into powder.
Embodiment 2: the preparation of porous magnetic polystyrene microsphere.
Specifically comprise the steps:
(1) get dry Fe prepared by 0.8g embodiment 13O4Magnetic nano-particle, joins 100ml50 (v/v) % ethanol waterIn solution, then, by ultrasonic mixed liquor processing 30min, drip gradually 1ml VTES to being dissolved with Fe3O4Suspension in. Afterwards, proceed in 250m1 three-neck flask, at N2Under protection, the ageing of 40 DEG C of rapid stirring 12h constant temperature.The product obtaining absolute ethanol washing three times, deionized water washed twice, 40 DEG C of vacuum drying, pulverize afterwardsEnd.
(2) get the BPO0.2g after powder 0.5g and the purifying that step (1) obtains, joined the benzene second that contains 6mlIn the test tube of alkene, 2ml toluene, 1ml normal heptane and 0.5mlDVB crosslinking agent, be placed in the ultrasonic mixing of ultrasonic wave 1h.
(3) measure deionized water 100ml in the beaker of 150ml, take respectively 0.6gPVP, 0.2gSDS adds itIn, with glass bar stirring, in ultrasonic wave, dissolve.
(4) oil-based liquid step (2) being obtained joins in the aqueous solution of step (3), is placed in processor for ultrasonic waveThe ultrasonic processing of 20KHz batch (-type) 5min, fully disperses, and pours the system obtaining into 100ml there-necked flask, 80 DEG C of waterBathe heating, after condensing reflux 2h, be warming up to 90 DEG C of reaction 6h, finally obtain micro-bluish violet suspension, respectively through magnetThe washing of magnetic separating alcohol, magnetic separates after pure water washing, and 40 DEG C of vacuum drying, grind to obtain brown color powdered product. To be driedSample carries out Soxhlet extracting 24h, and the solvent that Soxhlet extracting is used is the ethanolic solution that adds hydrochloric acid, the concentration of the hydrochloric acid addingBe 36 ~ 38wt%, the volume ratio of hydrochloric acid and ethanol is 1:75, and last vacuum drying can obtain product.
Embodiment 3:
Specifically comprise the steps:
(1) get dry Fe prepared by 1g embodiment 13O4Magnetic nano-particle, joins 100ml40 (v/v) % ethanol water-solubleIn liquid, then, by ultrasonic mixed liquor processing 20min, drip gradually 2ml VTES to being dissolved with Fe3O4Suspension in. Afterwards, proceed in 250m1 three-neck flask, at N2Under protection, the ageing of 50 DEG C of rapid stirring 24h constant temperature.The product obtaining absolute ethanol washing three times, deionized water washing three times, 60 DEG C of vacuum drying, pulverize afterwardsEnd.
(2) get the BPO0.17g after powder 0.34g and the purifying that step (1) obtains, joined the benzene that contains 8mlIn the test tube of ethene, 2ml toluene, 1ml normal heptane and 0.5mlDVB crosslinking agent, be placed in the ultrasonic mixing of ultrasonic wave 0.5h.
(3) measure deionized water 100ml in the beaker of 150ml, take respectively 0.8gPVP, 0.3gSDS adds itIn, with glass bar stirring, in ultrasonic wave, dissolve.
(4) oil-based liquid step (2) being obtained joins in the aqueous solution of step (3), is placed in processor for ultrasonic waveThe ultrasonic processing of 20KHz batch (-type) 10min, fully disperses, and pours the system obtaining into 100ml there-necked flask, 70 DEG C of waterBathe heating, after condensing reflux 1.5h, be warming up to 80 DEG C of reaction 8h, finally obtain micro-bluish violet suspension, respectively through magneticFerromagnetic separating alcohol washing, magnetic separates after pure water washing, and 40 DEG C of vacuum drying, grind to obtain brown color powdered product. To doDry sample carries out Soxhlet extracting 24h, and the solvent that Soxhlet extracting is used is the ethanolic solution that adds hydrochloric acid, the hydrochloric acid adding denseDegree is 36 ~ 38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:30, and last vacuum drying can obtain product.
Embodiment 4:
Specifically comprise the steps:
(1) get dry Fe prepared by 1.2g embodiment 13O4Magnetic nano-particle, joins 100ml60 (v/v) % ethanol waterIn solution, then, by ultrasonic mixed liquor processing 20min, drip gradually 2ml VTES to being dissolved with Fe3O4Suspension in. Afterwards, proceed in 250m1 three-neck flask, at N2Under protection, the ageing of 50 DEG C of rapid stirring 24h constant temperature.The product obtaining absolute ethanol washing 2 times, deionized water washing 3 times, 60 DEG C of vacuum drying afterwards, grind into powder.
(2) get the BPO0.15g after powder 0.5g and the purifying that step (1) obtains, joined the benzene second that contains 8mlIn the test tube of alkene, 2ml toluene, 1ml normal heptane and 0.5mlDVB crosslinking agent, be placed in the ultrasonic mixing of ultrasonic wave 0.5h.
(3) measure deionized water 200ml in the beaker of 500ml, take respectively 1gPVP, 0.3gSDS adds wherein,With glass bar stirring, in ultrasonic wave, dissolve.
(4) oil-based liquid step (2) being obtained joins in the aqueous solution of step (3), is placed in processor for ultrasonic waveThe ultrasonic processing of 20KHz batch (-type) 10min, fully disperses, and pours the system obtaining into 100ml there-necked flask, 70 DEG C of waterBathe heating, after condensing reflux 1.5h, be warming up to 80 DEG C of reaction 8h, finally obtain micro-bluish violet suspension, respectively through magneticFerromagnetic separating alcohol washing, magnetic separates after pure water washing, and 40 DEG C of vacuum drying, grind to obtain brown color powdered product. To doDry sample carries out Soxhlet extracting 24h, and the solvent that Soxhlet extracting is used is the ethanolic solution that adds hydrochloric acid, the hydrochloric acid adding denseDegree is 36 ~ 38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:30, and last vacuum drying can obtain product.
Claims (3)
1. the preparation method of porous magnetic polystyrene microsphere, is characterized in that, it comprises the steps:
(1) by dry Fe3O4Magnetic nano-particle joins in the aqueous solution of ethanol, after the ultrasonic processing 20～30min of ultrasonic cleaner, to Fe3O4In suspension, dropwise add VTES, then proceed in the lump in reactor, under nitrogen protection condition, stir ageing 12～24h, the Fe after the modification obtaining at 35～50 DEG C of constant temperature3O4Magnetic nano-particle through washing, vacuum drying, pulverize;
(2) get powder and the benzoyl peroxide mixing that step (1) obtains, add in the styrene solvent that contains pore-foaming agent and crosslinking agent, ultrasonic processing 0.5～1h, described pore-foaming agent is the mixture of first benzene and heptane, described crosslinking agent is divinylbenzene;
(3) by polyvinylpyrrolidone and lauryl sodium sulfate ultrasonic dissolution in water;
(4) liquid step (2) being obtained joins in the liquid that step (3) obtains, the ultrasonic processing 5～10min of large power supersonic instrument is to fully disperseing, the mixture obtaining is poured in reactor, after 70～80 DEG C of condensing reflux reaction 1.5～2h, be warming up to again 80～90 DEG C of condensing reflux reaction 6～8h, obtain suspension, wash through magnet magnetic separating alcohol, magnetic separates pure water washing again, brown color powdered product is ground to obtain in vacuum drying, brown color powdered product is carried out to Soxhlet extracting 24h, and last vacuum drying, to obtain final product;
In step (1), in the aqueous solution of ethanol, the concentration expressed in percentage by volume of ethanol is 40～60%;
In step (1), for the aqueous solution of 1L ethanol, dry Fe3O4It is 8～12g that magnetic nano-particle adds quality;
In step (1), for 1gFe3O4Magnetic nano-particle, the addition of VTES is 1mL～2mL;
In step (2), the powder that step (1) obtains and benzoyl peroxide in mass ratio 2～4:1 mix;
In step (2), the volume ratio 10～16:4:2:1 of styrene, toluene, normal heptane and divinylbenzene; The powder obtaining for every 1g step (1), the use volume of divinylbenzene is 1～1.5mL;
In step (3), the mass ratio of polyvinylpyrrolidone, lauryl sodium sulfate and water is 5～8:1～3:1000; The mass ratio of the powder that polyvinylpyrrolidone and step (1) obtain is 1～2:1.
2. the preparation method of porous magnetic polystyrene microsphere according to claim 1, it is characterized in that, in step (4), in Soxhlet extracting, the solvent using is the ethanolic solution that adds hydrochloric acid, the concentration of the hydrochloric acid adding is 36～38wt%, and the volume ratio of hydrochloric acid and ethanol is 1:75～1:30.
3. the porous magnetic polystyrene microsphere that in claim 1～2, any one prepares.
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| CN102964539B true CN102964539B (en) | 2016-05-25 |
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| CN103212352B (en) * | 2013-05-02 | 2014-12-03 | 黑龙江大学 | Preparation method of magnetic microspheres |
| CN103588919A (en) * | 2013-10-31 | 2014-02-19 | 江苏大学 | Preparation method of magnetic porous adsorbent by suspension polymerization |
| CN104829768A (en) * | 2015-05-12 | 2015-08-12 | 南京理工大学 | Preparation method of low-density bulk magnetic polystyrene oil absorption material |
| CN105803795A (en) * | 2016-04-21 | 2016-07-27 | 安徽皖翎羽绒制品有限公司 | Water-borne polyurethane coating agent containing superfine down fiber-porous polystyrene microspheres |
| CN108311067B (en) * | 2017-01-16 | 2020-06-02 | 中国科学院理化技术研究所 | Oil-water microemulsion separation method based on composite Janus microspheres |
| CN106669634B (en) * | 2017-01-25 | 2019-12-27 | 中国科学院过程工程研究所 | Magnetic extraction resin and preparation method and application thereof |
| CN107033050B (en) * | 2017-05-04 | 2019-03-22 | 江苏强盛功能化学股份有限公司 | A kind of processing method of contaminated BPO |
| CN107267494A (en) * | 2017-05-23 | 2017-10-20 | 陕西师范大学 | The@Fe of enzyme@ZIF 83O4Magnetic Nano enzyme reactor and preparation method thereof |
| CN107973872B (en) * | 2017-12-11 | 2020-12-22 | 西南科技大学 | Preparation method of nano ferroferric oxide doped styrene-divinylbenzene copolymer hydrophobic catalyst carrier |
| CN110003517A (en) * | 2019-04-04 | 2019-07-12 | 河北科技大学 | A kind of modified porous Magnetic Polystyrene Microsphere and preparation method thereof |
| CN110294816B (en) * | 2019-06-06 | 2021-07-16 | 东莞东阳光科研发有限公司 | Magnetic nano polystyrene carboxyl microsphere and preparation method thereof |
| CN111138611A (en) * | 2020-01-06 | 2020-05-12 | 河北科技大学 | Preparation method and application of magnetic sulfonated polystyrene molecular brush |
| CN114106266A (en) * | 2021-11-25 | 2022-03-01 | 东南大学 | Raspberry-shaped magnetic polystyrene microsphere and preparation method thereof |
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